Accurate and Efficient SIMS Oxygen Isotope Analysis of Composition-Variable Minerals: Online Matrix Effect Calibration for Dolomite.

High-quality oxygen isotope analysis of composition-variable minerals (e.g., ubiquitous carbonates) using secondary ion mass spectrometry (SIMS) is extremely challenging. The classical off-line procedure, which requires additional electron probe microanalyzer (EPMA) chemical compositions for calibrating instrumental mass fractionation (IMF), is inherently inaccurate and analytically inefficient. In this study, the first accurate and paired SIMS analysis of δ18O and Fe# [molar Fe/(Mg + Fe)] in dolomite is reported. Based on five newly developed dolomite O-isotopic standards with an Fe# range of 0.01-0.35 obtained by SIMS, a novel accurate and rapid online matrix effect calibration method for dolomite O-isotope analysis was developed using concurrent SIMS 18O-16O-56Fe16O-24Mg16O measurements without additional chemical electron probe microanalysis. A logistic equation was proposed as the best-fit curve to represent the δ18O matrix effect based on the 56Fe16O/24Mg16O ratios. For CTD-4 carbonatitic dolomite with variable Fe# but homogeneous oxygen isotopes, the off-line method exhibited highly variable apparent δ18O values in the range of 5.74-10.11‰. The online method yielded a homogeneous δ18O value of 7.94 ± 0.34‰ (2SD, n = 40), which is comparable with that of bulk analysis (7.94 ± 0.20‰; 2SD). Comprehensive analyses validated the online method as the best strategy for performing accurate δ18O analysis of samples with highly heterogeneous compositions. Based on its accuracy, simplicity, and economic feasibility, this method has potential applications in the analysis of composition-complex dolomites, detrital dolomites, and other precious terrestrial and extraterrestrial materials.

Capabilities of through-the-substrate microdiffraction: application of Patterson-function direct methods to synchrotron data from polished thin sections.

Some theoretical and practical aspects of the application of transmission microdiffraction (µXRD) to thin sections (≤30 µm thickness) of samples fixed or deposited on substrates are discussed. The principal characteristic of this technique is that the analysed micro-sized region of the thin section is illuminated through the substrate (tts-µXRD). Fields that can benefit from this are mineralogy, petrology and materials sciences since they often require in situ lateral studies to follow the evolution of crystalline phases or to determine new crystal structures in the case of phase transitions. The capability of tts-µXRD for performing structural studies with synchrotron radiation is shown by two examples. The first example is a test case in which tts-µXRD intensity data of pure aerinite are processed using Patterson-function direct methods to directly solve the crystal structure. In the second example, tts-µXRD is used to study the transformation of laumonite into a new aluminosilicate for which a crystal structure model is proposed.

Light oxygen isotopes in mantle-derived magmas reflect assimilation of sub-continental lithospheric mantle material.

Oxygen isotope ratios in mantle-derived magmas that differ from typical mantle values are generally attributed to crustal contamination, deeply subducted crustal material in the mantle source or primordial heterogeneities. Here we provide an alternative view for the origin of light oxygen-isotope signatures in mantle-derived magmas using kimberlites, carbonate-rich magmas that assimilate mantle debris during ascent. Olivine grains in kimberlites are commonly zoned between a mantle-derived core and a magmatic rim, thus constraining the compositions of both mantle wall-rocks and melt phase. Secondary ion mass spectrometry (SIMS) analyses of olivine in worldwide kimberlites show a remarkable correlation between mean oxygen-isotope compositions of cores and rims from mantle-like 18O/16O to lower 'crustal' values. This observation indicates that kimberlites entraining low-18O/16O olivine xenocrysts are modified by assimilation of low-18O/16O sub-continental lithospheric mantle material. Interaction with geochemically-enriched domains of the sub-continental lithospheric mantle can therefore be an important source of apparently 'crustal' signatures in mantle-derived magmas.